EP0045840A1 - Method to prepare solutions of cationic polyazo dyestuffs - Google Patents
Method to prepare solutions of cationic polyazo dyestuffs Download PDFInfo
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- EP0045840A1 EP0045840A1 EP81104886A EP81104886A EP0045840A1 EP 0045840 A1 EP0045840 A1 EP 0045840A1 EP 81104886 A EP81104886 A EP 81104886A EP 81104886 A EP81104886 A EP 81104886A EP 0045840 A1 EP0045840 A1 EP 0045840A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B41/00—Special methods of performing the coupling reaction
- C09B41/006—Special methods of performing the coupling reaction characterised by process features
- C09B41/009—Diazotising and coupling in one step
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B37/00—Azo dyes prepared by coupling the diazotised amine with itself
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S534/00—Organic compounds -- part of the class 532-570 series
- Y10S534/01—Mixtures of azo compounds
Definitions
- the dyes of the formula I have long been known under the names Bismarckbraun and Vesuvin. It is prepared by reacting the hydrochloric acid solution of m-phenylenediamine with sodium nitrite. Here, the development of nitrogen with the formation of very basic compounds and also the coupling to higher molecular weight, insoluble dyes is observed as a side reaction (E. Täuber and F. Walder, B 30, 2 111, 2 899, B 33, 2 897). Dyes produced in this way are only suitable for the preparation of dye solutions after prior cleaning. The formation of higher molecular weight products can be avoided if the coupling is carried out in the presence of large amounts of sodium chloride (US Pat. No. 2,022,606).
- This highly saline dye requires further cleaning operations to produce a concentrated dye solution.
- it can be freed from salt by passing the solution under pressure one or more times over a semi-permeable membrane is, which lets water and salt through, while dyes are retained (DE-AS 2 204 725, Example 9).
- the dye is first transferred to the dye base by a further process already described and then dissolved in a mixture of glacial acetic acid and diethylene glycol monobutyl ether (US Pat. No. 3,346,322, Example 12).
- the hue of the dyeings on paper can be nuanced in the desired manner by mixing coupling with the aromatic monoamines.
- Aniline gives yellow shades, while p-toluidine, p-anisidine and p-phenetidine give red tones.
- the aqueous sodium nitrite solution is dropped in below the surface of the solution of the aromatic amino compounds in aliphatic carboxylic acids. This practically completely prevents the formation of higher molecular dye components that lead to solution instability.
- the solutions can also contain additions of organic solvents, for example ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl glycol acetate, ethyl glycol acetate, glycol diacetate, monoacetin, triacetin, oxypropionitrile, urea, dimethlyl urea, tetramethyl-uronol, tetramethyl-uronol, tetramethyl-uronol, tetramethyl-uronol, tetramethyl-uronol, tetramethylrolidone Ethylene carbonate, propylene carbonate, caprolactam and their mixtures.
- the cold stability of the solutions can be improved even more.
- the dye solutions preferably contain 5-30% by weight of the solvents specified above.
- oxidizing agents such as H 2 O 2
- H 2 O 2 oxidizing agents
- 0.5-2% by weight H 2 O 2 is preferably added to the dye solutions.
- the dye solutions prepared according to the invention are used for dyeing cellulose material, in particular paper.
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Abstract
Zur Herstellung konzentrierter Lösungen von kationischen Polyazofarbstoffen der Formel
- R für Wasserstoff oder Methyl und
- R' für einen gegebenenfalls durch Hydroxy, Alkoxy oder Halogen substituierten Alkylrest mit 1 bis 3 Kohlenstoffatomen stehen,
- und deren Mischkupplungsprodukte mit aromatischen Monoaminen, werden Diaminobenzole der allgemeinen Formel
- R die oben angegebene Bedeutung hat, gegebenenfalls in Mischung mit bis zu 30 Mol% aromatischen Monoaminen der Formel
- R2 für Wasserstoff, Halogen, C1-bis C4-Alkyl, C,-bis C4-Alkoxy und C1-bis C4-Acylamino steht und
- n 1 bis 3 bedeutet, in aliphatischen Carbonsäuren mit 2 bis 4 Kohlenstoffatomen, die gegebenenfalls durch Halogen, Hydroxy oder Alkoxy substituiert sein können, gelöst und bei 0 bis 30°C mit 0,5 bis 0,75 mol eines Salzes oder Esters der salpetrigen Säure pro mol Diamin umgesetzt.
- R represents hydrogen or methyl and
- R 'represents an alkyl radical with 1 to 3 carbon atoms which is optionally substituted by hydroxyl, alkoxy or halogen,
- and their mixed coupling products with aromatic monoamines become diaminobenzenes of the general formula
- R has the meaning given above, optionally in a mixture with up to 30 mol% of aromatic monoamines of the formula
- R 2 represents hydrogen, halogen, C 1 to C 4 alkyl, C, to C 4 alkoxy and C 1 to C 4 acylamino and
- n is 1 to 3, dissolved in aliphatic carboxylic acids with 2 to 4 carbon atoms, which may optionally be substituted by halogen, hydroxy or alkoxy, and at 0 to 30 ° C. with 0.5 to 0.75 mol of a salt or ester of nitrous oxide Acid per mole of diamine converted.
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung konzentrierter Lösungen von kationischen Polyazofarbstoffen der Formel
- R für Wasserstoff oder Methyl und
- R1 für einen gegebenenfalls durch Hydroxy, Alkoxy oder Halogen substituierten Alkylrest mit 1 bis 3 Kohlenstoffatomen stehen,
- Rdie oben angegebene Bedeutung hat,
- gegebenenfalls in Mischung mit bis zu 3.0 Mol% aromatischen Monoaminen der Formel
- R 2 für Wasserstoff, Halogen, C1- bis C4-Alkyl, C1- bis C4-Alkoxy und C1- bis C4-Acylamino steht und
- n 1 bis 3 bedeutet,
- in aliphatischen Carbonsäuren mit 2 bis 4 Kohlenstoffatomen, die gegebenenfalls durch Halogen, Hydroxy oder Alkoxy substituiert sein können, löst und bei 0 bis 30°C mit 0,5 bis 0,75 mol eines Salzes oder Esters der salpetrigen Säure pro mol Diamin umsetzt.
- R represents hydrogen or methyl and
- R 1 represents an alkyl radical with 1 to 3 carbon atoms which is optionally substituted by hydroxyl, alkoxy or halogen,
- R has the meaning given above,
- optionally in a mixture with up to 3.0 mol% of aromatic monoamines of the formula
- R 2 represents hydrogen, halogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy and C 1 - to C 4 -acylamino and
- n means 1 to 3,
- in aliphatic carboxylic acids with 2 to 4 carbon atoms, which may optionally be substituted by halogen, hydroxy or alkoxy, and reacted at 0 to 30 ° C with 0.5 to 0.75 mol of a salt or ester of nitrous acid per mol of diamine.
Die Farbstoffe der Formel I sind unter dem Namen Bismarckbraun und Vesuvin seit langem bekannt. Man stellt sie durch Umsetzung der salzsauren Lösung von m-Phenylendiamin mit Natriumnitrit her. Hierbei wird die Entwicklung von Stickstoff unter Bildung sehwzch basischer Verbindungen und außerdem die Kupplung zu höhermolekularen, unlöslichen Farbstoffen als Nebenreaktion beobachtet (E. Täuber und F. Walder, B 30, 2 111, 2 899, B 33, 2 897). So hergestellte Farbstoffe sind erst nach vorheriger Reinigung zur Herstellung von Farbstofflösungen geeignet. Die Bildung höhermolekularer Produkte läßt sich vermeiden, wenn man die Kupplung in Gegenwart großer Mengen von Kochsalz vornimmt (US-PS 2 022 606). Dieser stark salzhaltige Farbstoff erfordert zur Eerstel- 'lung einer konzentrierten Farbstofflösung weitere Reinigungsoperationen. Beispielsweise kann er vom Salz befreit werden, indem die Lösung unter Druck ein- oder mehrmals über eine halbdurchlässige Membran geleitet wird, die Wasser und Salz hindurchläßt, während Farbstoffe zurückgehalten werden (DE-AS 2 204 725, Beispiel 9). Zur Herstellung einer Lösung führt man nach einem weiteren bereits beschriebenen Verfahren den Farbstoff zunächst in die Farbbase über und löst diese dann in einem Gemisch von Eisessig und Diethylenglykolmonobutylether ( US-PS 3,346,322, Beispiel 12). Bei der Diazotierung von m-Phenylendiamin in aliphatischen Carbonsäuren mit Natriumnitrit im Molverhältnis 1/2 entsteht ein komplexes Gemisch von Diazoniumsalz, Diazoaminoverbindung, Mono- und Bisazofarbstoffen, das nicht für Färbezwecke einsetzbar ist (B. I. Belov und V. V. Kozlov, Zh. Obsh. Khim., Vol. 32., Nr. 10, S. 3 362 - 3 368). Nach diesem Stand der Technik war nicht zu erwarten, daß das erfindungsgemäße Verfahren zu stabilen Farbstofflösungen führen würde, die sich hervorragend zum Färben von holzschliffhaltigem Papier eignen.The dyes of the formula I have long been known under the names Bismarckbraun and Vesuvin. It is prepared by reacting the hydrochloric acid solution of m-phenylenediamine with sodium nitrite. Here, the development of nitrogen with the formation of very basic compounds and also the coupling to higher molecular weight, insoluble dyes is observed as a side reaction (E. Täuber and F. Walder, B 30, 2 111, 2 899, B 33, 2 897). Dyes produced in this way are only suitable for the preparation of dye solutions after prior cleaning. The formation of higher molecular weight products can be avoided if the coupling is carried out in the presence of large amounts of sodium chloride (US Pat. No. 2,022,606). This highly saline dye requires further cleaning operations to produce a concentrated dye solution. For example, it can be freed from salt by passing the solution under pressure one or more times over a semi-permeable membrane is, which lets water and salt through, while dyes are retained (DE-AS 2 204 725, Example 9). To prepare a solution, the dye is first transferred to the dye base by a further process already described and then dissolved in a mixture of glacial acetic acid and diethylene glycol monobutyl ether (US Pat. No. 3,346,322, Example 12). The diazotization of m-phenylenediamine in aliphatic carboxylic acids with sodium nitrite in a molar ratio of 1/2 results in a complex mixture of diazonium salt, diazoamino compound, mono- and bisazo dyes, which cannot be used for dyeing purposes (BI Belov and VV Kozlov, Zh. Obsh. Khim. , Vol. 32, No. 10, pp. 3 362 - 3 368). According to this prior art, it was not to be expected that the process according to the invention would lead to stable dye solutions which are outstandingly suitable for dyeing paper containing pulp.
Geeignete Diamine der allgemeinen Formel II sind:
- 1,3-Diamino-benzol, 2,4-Diaminc-toluol, 2,6-Diamino-toluol und Mischungen dieser Diamine in jedem Molverhältnis.
- 1,3-diamino-benzene, 2,4-diaminotoluene, 2,6-diamino-toluene and mixtures of these diamines in any molar ratio.
Geeignete aromatische Monoamine der Formel III sind:
- Anilin, 2-Toluidin, 3-Toluidin, 4-Toluidin, 4-Amino-1,3-dimethyl-benzol, 2-Anisidin, 3-Anisidin, 4-Anisidin, 2-Phenetidin, 4-Phenetidin, 2-(4-Amino-phenoxy)-ethanol, 2-Chlor-anilin, 4-Chlor-anilin, 2,4-Dichlor-anilin und 4-Amino-acetanilid.
- Aniline, 2-toluidine, 3-toluidine, 4-toluidine, 4-amino-1,3-dimethyl-benzene, 2-anisidine, 3-anisidine, 4-anisidine, 2-phenetidine, 4-phenetidine, 2- (4th -Amino-phenoxy) -ethanol, 2-chloro-aniline, 4-chloro-aniline, 2,4-dichloro-aniline and 4-amino-acetanilide.
Durch Mischkupplung mit den arcmatischen Monoaminen läßt sich der Farbton der Färbungen auf Papier in gewünschter Weise nuancieren. Mit Anilin erhält man gelbere Farbt5ne, mit p-Toluidin, p-Anisidin und p-Phenetidin rötere Farbtöne.The hue of the dyeings on paper can be nuanced in the desired manner by mixing coupling with the aromatic monoamines. Aniline gives yellow shades, while p-toluidine, p-anisidine and p-phenetidine give red tones.
Als aliphatische Carbonsäuren eignen sich:
- Essigsäure, Propionsäure, 2-Chlor-propionsäure, Glykolsäure, Ethoxyessigsäure, Mono-, Di- und Trichloressigsäure und Milchsäure Bevorzugt wird Essigsäure verwendet.
- Acetic acid, propionic acid, 2-chloropropionic acid, glycolic acid, ethoxyacetic acid, mono-, di- and trichloroacetic acid and lactic acid. Acetic acid is preferably used.
Nach einer bevorzugten Verfahrensweise wird die wäßrige Natriumnitritlösung unter die Oberfläche der Lösung der aromatischen Aminoverbindungen in aliphatischen Carbonsäuren eingetropft. Hierdurch wird die Bildung höhermolekularer Farbstoffanteile, die zur Lösungsinstabilität führen praktisch vollständig vermieden.According to a preferred procedure, the aqueous sodium nitrite solution is dropped in below the surface of the solution of the aromatic amino compounds in aliphatic carboxylic acids. This practically completely prevents the formation of higher molecular dye components that lead to solution instability.
Der gleiche Effekt wird erreicht, wenn man nach einer weiteren bevorzugten Verfahrensvariante zur Lösung des aromatischen Amins in der aliphatischen Carbonsäure festes Natriumnitrit zugibt und anschließend Wasser eintropft.The same effect is achieved if, according to a further preferred process variant, solid sodium nitrite is added to the solution of the aromatic amine in the aliphatic carboxylic acid and water is then added dropwise.
Die Lösungen können auch Zusätze organischer Lösungsmittel enthalten, beispielsweise Ethylenglykol, Propylenglykol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonobutylether, Methylglykolacetat, Ethylglykolacetat, Glykoldiacetat, Monoacetin, Triacetin, Oxypropionitril, Harnstoff, Dimethvlharnstoff, Tetramethylharnstoff, Thioharnstoff, Tetramethylensulfon, Pyrrolidon, N-Methyl-pyrrolidon, Ethylencarbonat, Propylencarbonat, Caprolactam und ihre Gemische. Die Kältestabilität der Lösungen kann hierdurch noch verbessert werden. Bevorzugt enthalten die Farbstofflösungen 5 - 30 Gew.-% der oben angegebenen Lösungsmittel.The solutions can also contain additions of organic solvents, for example ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl glycol acetate, ethyl glycol acetate, glycol diacetate, monoacetin, triacetin, oxypropionitrile, urea, dimethlyl urea, tetramethyl-uronol, tetramethyl-uronol, tetramethyl-uronol, tetramethyl-uronol, tetramethylrolidone Ethylene carbonate, propylene carbonate, caprolactam and their mixtures. The cold stability of the solutions can be improved even more. The dye solutions preferably contain 5-30% by weight of the solvents specified above.
In einigen Fällen hat sich ein Zusatz von Oxidationsmitteln,wie H2O2, zur Stabilisierung der Lösungen bei höheren Temperaturen als vorteilhaft erwiesen. Dabei werden den Farbstofflösungen vorzugsweise 0,5 - 2 Gew.-% H2O2 zugesetzt.In some cases, the addition of oxidizing agents, such as H 2 O 2 , has proven to be advantageous for stabilizing the solutions at higher temperatures. In this case, 0.5-2% by weight H 2 O 2 is preferably added to the dye solutions.
Die erfindungsgemäß hergestellten Farbstofflösungen finden Verwendung zum Färben von Cellulosematerial insbesondere Papier.The dye solutions prepared according to the invention are used for dyeing cellulose material, in particular paper.
24,4 g 2,4-Diamino-toluol werden in 60 ml Eisessig bei 50°C gelöst. Nach Abkühlen auf 5°C tropft man eine Lösung von 8,8 g Natriumnitrit in 30 ml Wasser bei 0 - 5°C unter die Oberfläche ein. Die dunkelbraune Lösung läßt man noch einige Stunden bei Raumtemperatur nachrühren und filtriert sie. Auf dem Filter verbleibt praktisch kein Rückstand. Holzschliffhaltiges Papier wird rotbraun angefärbt.24.4 g of 2,4-diamino-toluene are dissolved in 60 ml of glacial acetic acid at 50 ° C. After cooling to 5 ° C., a solution of 8.8 g of sodium nitrite in 30 ml of water is added dropwise at 0-5 ° C. below the surface. The dark brown solution is allowed to stir for a few more hours at room temperature and filtered. There is practically no residue on the filter. Paper containing wood pulp is dyed red-brown.
In eine Lösung von 30 g Caprolactam in 295 g Eisessig läßt man 122. g eines geschmolzenen Amingemisches, bestehend aus 65 % 2,4-Diamino-toluol und 35 % 2,6-Diamino-toluol, einlaufen. Die 65 - 70°C heiße Lösung wird auf 5°C abgekühlt und mit 46 g Natriumnitrit versetzt. Dann läßt man innerhalb von 3 h bei 0 - 10°C 45 ml Wasser langsam zulaufen und rührt 2 h nach. Holzschliffhaltiges Papier wird von dieser Lösung gelbstichig braun angefärbt.122. g of a molten amine mixture consisting of 65% 2,4-diamino-toluene and 35% 2,6-diamino-toluene are run into a solution of 30 g of caprolactam in 295 g of glacial acetic acid. The 65-70 ° C solution is cooled to 5 ° C and 46 g of sodium nitrite are added. Then 45 ml of water are allowed to run in slowly at 0-10 ° C. in the course of 3 hours and the mixture is subsequently stirred for 2 hours. Wood pulp-containing paper is stained yellowish brown by this solution.
220 g 2,4-Diamino-toluol werden in 1 000 ml Eisessig gelöst und 19 g Anilin zugesetzt. Nach Abkühlen auf 5°C tropft man innerhalb von 2 h bei 0 - 5°C 88 g Natriumnitrit, gelöst in 300 ml Wasser, ein. Nach mehrstündigem Nachrühren erhält man eine rückstandsfreie Farbstofflösung, die holzschliffhaltiges Papier in einem klaren Braun färbt.220 g of 2,4-diamino-toluene are dissolved in 1,000 ml of glacial acetic acid and 19 g of aniline are added. After cooling to 5 ° C., 88 g of sodium nitrite, dissolved in 300 ml of water, are added dropwise at 0 ° -5 ° C. in the course of 2 h. After stirring for several hours, a residue-free dye solution is obtained, which dyes wood pulp-containing paper in a clear brown.
Verwendet man anstelle von 19 g Anilin 24,6 g 4-Anisidin und verfährt sonst in gleicher Weise, so erhält man eine Farbstofflösung, die holzschliffhaltiges Papier in einem rotstichigen Braun anfärbt.If 24.6 g of 4-anisidine are used instead of 19 g of aniline and the procedure is otherwise the same, a dye solution is obtained which stains wood-pulped paper in a reddish brown.
22 g 2,4-Diamino-toluol werden in 100 ml Propionsäure gelöst und 1,9 g Anilin zugesetzt. Nach Abkühlen auf 5°C tropft man in die Lösung 8,8 g Natriumnitrit, gelöst in 30 ml Wasser, innerhalb von 2 h bei 0 - 5°C ein.22 g of 2,4-diamino-toluene are dissolved in 100 ml of propionic acid and 1.9 g of aniline are added. After cooling to 5 ° C., 8.8 g of sodium nitrite, dissolved in 30 ml of water, are added dropwise to the solution at 0-5 ° C. in the course of 2 hours.
- 6 - Nach mehrstündigem Nachrühren erhält man eine Farbstofflösung, die holzschliffhaltiges Papier braun färbt.- 6 - After stirring for several hours, a dye solution is obtained, which stains paper containing wood pulp brown.
Mit gleichem Erfolg läßt sich anstelle von Propionsäure auch die gleiche Menge 2-Chlor-propionsäure, Ethoxyessigsäure oder Milchsäure verwenden.The same amount of 2-chloropropionic acid, ethoxyacetic acid or lactic acid can be used instead of propionic acid with the same success.
10,8 g 1,3-Diamino-benzol und 12,2 g 2,4-Diamino-toluol werden in 100 ml Eisessig gelöst und die Lösung auf 5°C abgekühlt. Bei 0 - 5°C tropft man eine Lösung von 10 g Natriumnitrit in 30 ml Wasser innerhalb von 2 h ein und läßt 6 h nachrühren. Die Farbstofflösung färbt holzschliffhaltiges Papier braun.10.8 g of 1,3-diamino-benzene and 12.2 g of 2,4-diamino-toluene are dissolved in 100 ml of glacial acetic acid and the solution is cooled to 5 ° C. A solution of 10 g of sodium nitrite in 30 ml of water is added dropwise at 0 ° -5 ° C. in the course of 2 hours and the mixture is subsequently stirred for 6 hours. The dye solution stains wood pulp-containing paper brown.
9,7 g 1,3-Diamino-benzol und 11,0 g 2,4-Diamino-toluol werden in 100 ml Eisessig gelöst und 2,14 g 2-Toluidin zugesetzt. Dann kühlt man die Lösung auf 5°C ab und läßt .. eine Lösung von 8,8 g Natriumnitrit in 30 ml Wasser bei 0 - 5°C innerhalb von 2 h eintropfen. Nach mehrstündigem Nachrühren erhält man eine Farbstofflösung, die holzschliffhaltiges Papier braun färbt.9.7 g of 1,3-diamino-benzene and 11.0 g of 2,4-diamino-toluene are dissolved in 100 ml of glacial acetic acid and 2.14 g of 2-toluidine are added. Then the solution is cooled to 5 ° C. and a solution of 8.8 g of sodium nitrite in 30 ml of water is added dropwise at 0-5 ° C. in the course of 2 hours. After stirring for several hours, a dye solution is obtained which stains paper containing wood pulp brown.
Mit gleichem Erfolg lassen sich anstelle von 2,14 g 2-Toluidin auch 2,46 g 2-Anisidin, 2,54 g 2-Chlor-anilin, 2,54 g 4-Chlor-anilin, 3,24 g 2,4-Dichlor-anilin oder 2,74 g 2-?henetidin einsetzen.Instead of 2.14 g of 2-toluidine, 2.46 g of 2-anisidine, 2.54 g of 2-chloro-aniline, 2.54 g of 4-chloro-aniline and 3.24 g of 2.4 can be used with the same success -Dichloro-aniline or 2.74 g of 2-? Henetidine.
9,7 g 1,3-Diamino-benzol und 11,0 g 2,4-Diamino-toluol werden in 100 ml Eisessig gelöst und 2,46 g 4-Anisidin zugesetzt. Nach Abkühlen auf 5°C tropft man eine Lösung von 8,8 g Natriumnitrit in 30 ml Wasser bei 0 - 5°C unter Kühlen ein. Nach mehrstündigem Rühren erhält man eine Farbstofflösung, die holzschliffhaltiges Papier rotstichig braun anfärbt.9.7 g of 1,3-diamino-benzene and 11.0 g of 2,4-diamino-toluene are dissolved in 100 ml of glacial acetic acid and 2.46 g of 4-anisidine are added. After cooling to 5 ° C., a solution of 8.8 g of sodium nitrite in 30 ml of water is added dropwise at 0-5 ° C. with cooling. After stirring for several hours, a dye solution is obtained which stains wood pulp-containing paper reddish brown.
Mit gleichem Erfolg lassen sich anstelle von 2,46 g 4-Anisidin auch 2,74 g 4-Phenetidin, 3,06 g 2-(4-Amino-phenoxy)-ethanol oder 3,0 g 4-Amino-acetanilid einsetzen.Instead of 2.46 g of 4-anisidine, 2.74 g of 4-phenetidine, 3.06 g of 2- (4-aminophenoxy) ethanol or 3.0 g of 4-aminoacetanilide can be used with the same success.
21,6 g 1,3-Diamino-benzol werden in 100 ml Eisessig gelöst, wobei die Temperatur bis auf 32°C ansteigt. Nach Abkühlen auf 5°C tropft man eine Lösung von 7,3 g Natriumnitrit, gelöst in 30 ml Wasser, unter Kühlen bei 0 - 50C ein. Man läßt 4 h bei Raumtemperatur nachrühren und saugt die Lösung ab. Auf dem Filter verbleibt kein Rückstand. Holzschliffhaltiges Papier wird von dieser Lösung braun gefärbt.21.6 g of 1,3-diamino-benzene are dissolved in 100 ml of glacial acetic acid, the temperature rising to 32 ° C. After cooling to 5 ° C is added dropwise a solution of 7.3 g of sodium nitrite dissolved in 30 ml of water under cooling at 0 - 5 0 C a. The mixture is stirred for 4 h at room temperature and the solution is filtered off with suction. There is no residue on the filter. Wood pulp-containing paper is colored brown by this solution.
22 g 2,6-Diamino-toluol werden in 100 ml Eisessig bei 70°C gelöst und auf 0 - 5°C abgekühlt. Man setzt 1,9 g Anilin zu und tropft dann bei 0 - 5°C eine Lösung von 8,8 g Natriumnitrit in 30 ml Wasser unter die Oberfläche ein. Nach mehrstündigem Rühren bei Raumtemperatur erhält man eine klare Lösung, die holzschliffhaltiges Papier gelbstichig braun anfärbt.22 g of 2,6-diamino-toluene are dissolved in 100 ml of glacial acetic acid at 70 ° C and cooled to 0 - 5 ° C. 1.9 g of aniline are added, and a solution of 8.8 g of sodium nitrite in 30 ml of water is then added dropwise at 0-5 ° C. below the surface. After stirring for several hours at room temperature, a clear solution is obtained which stains wood-pulped paper yellowish brown.
81,3 g eines Gemisches, bestehend aus 65 % 2,4-Diamino-toluol und 35 % 2,6-Diamino-toluol, und 31 g Anilin werden in 240 ml Eisessig und 30 g L-Caprolactam unter Erwärmen auf ca. 70°C gelöst. Nach Abkühlen auf 5°C werden innerhalb von 2 h 46 g Natriumnitrit, gelöst in 55,5 ml Wasser, zugetropft. Man rührt bei 5 - 10°C über Nacht nach und setzt dann 10 ml 30%ige H2O2-Lösung hinzu. 81, 3 g of a mixture consisting of 65% 2,4-diaminotoluene and 35% 2,6-diamino-toluene and 31 g of aniline in 240 ml of glacial acetic acid and 30 g L-caprolactam were heated to about 70 ° C solved. After cooling to 5 ° C., 46 g of sodium nitrite, dissolved in 55.5 ml of water, are added dropwise within 2 h. The mixture is stirred at 5-10 ° C. overnight and 10 ml of 30% H 2 O 2 solution are then added.
66,6 g 1,3-Diamino-benzol und 31 g Anilin werden in 240 ml Eisessig und 30 g ε-Caprolactam bei Raumtemperatur gelöst. Nach Abkühlen auf 5°C tropft man innerhalb von 2 h eine Lösung von 46 g Natriumnitrit in 55,5 ml Wasser hinzu und rührt über Nacht bei 5 - 10°C nach. Anschließend werden 10 ml 30%ige H2O2-Lösung zugesetzt.66.6 g of 1,3-diamino-benzene and 31 g of aniline are dissolved in 240 ml of glacial acetic acid and 30 g of ε-caprolactam at room temperature. After cooling to 5 ° C., a solution of 46 g of sodium nitrite in 55.5 ml of water is added dropwise over the course of 2 hours, and the mixture is subsequently stirred at 5-10 ° C. overnight. Then 10 ml of 30% H 2 O 2 solution are added.
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3025557 | 1980-07-05 | ||
| DE19803025557 DE3025557A1 (en) | 1980-07-05 | 1980-07-05 | SOLUTION OF CATIONIC POLYAZO DYES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0045840A1 true EP0045840A1 (en) | 1982-02-17 |
| EP0045840B1 EP0045840B1 (en) | 1983-09-21 |
Family
ID=6106511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81104886A Expired EP0045840B1 (en) | 1980-07-05 | 1981-06-24 | Method to prepare solutions of cationic polyazo dyestuffs |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4400321A (en) |
| EP (1) | EP0045840B1 (en) |
| JP (1) | JPS5744668A (en) |
| BR (1) | BR8104262A (en) |
| DE (2) | DE3025557A1 (en) |
| ES (1) | ES8205254A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0115818A2 (en) * | 1983-02-03 | 1984-08-15 | Bayer Ag | Cationic polyazo-dyestuffs, their stabilized solutions, their preparation and use |
| EP0341325A1 (en) * | 1988-05-07 | 1989-11-15 | BASF Aktiengesellschaft | Process for the manufacture of liquid preparations of basic azodyes |
| WO2005113681A1 (en) * | 2004-05-19 | 2005-12-01 | Basf Aktiengesellschaft | Method for producing a liquid formulation of salts of sulphonic-acid azo dyes |
| WO2005113682A1 (en) * | 2004-05-19 | 2005-12-01 | Basf Aktiengesellschaft | Method for producing liquid adjustments of basic azo dyes |
| US7488810B2 (en) | 2002-11-28 | 2009-02-10 | Basf Aktiengesellschaft | Method for producing a liquid formulation of salts of sulfoacidic azo dyes |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923972A (en) * | 1987-04-23 | 1990-05-08 | Basf Aktiengesellschaft | Preparation of liquid formulations of basic azo dyes in carboxylic acid solution and subsequent heating |
| GB9514386D0 (en) * | 1995-07-13 | 1995-09-13 | Zeneca Ltd | Stabilised dye composition |
| JP3247941B2 (en) | 1997-10-31 | 2002-01-21 | 日本鋼管株式会社 | Plate for sliding nozzle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2022606A (en) * | 1934-06-08 | 1935-11-26 | Du Pont | Brown disazo dyes |
| FR1355911A (en) * | 1962-03-29 | 1964-03-20 | Basf Ag | Highly concentrated solutions of basic dyes with good stability |
| EP0036553A1 (en) * | 1980-03-22 | 1981-09-30 | BASF Aktiengesellschaft | Method of preparing liquid compositions of basic azo dyestuffs |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941768A (en) * | 1968-05-30 | 1976-03-02 | Ciba-Geigy Ag | One step diazotization coupling process |
| US3793305A (en) * | 1970-09-14 | 1974-02-19 | Du Pont | One-step process of preparing azo dyes by simultaneous diazotization |
| DE2209478C3 (en) * | 1972-02-29 | 1975-04-10 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of concentrated solutions of metal-free anionic azo dyes containing sulfonic acid groups |
-
1980
- 1980-07-05 DE DE19803025557 patent/DE3025557A1/en not_active Withdrawn
-
1981
- 1981-06-17 US US06/274,338 patent/US4400321A/en not_active Expired - Fee Related
- 1981-06-24 EP EP81104886A patent/EP0045840B1/en not_active Expired
- 1981-06-24 DE DE8181104886T patent/DE3160953D1/en not_active Expired
- 1981-07-03 BR BR8104262A patent/BR8104262A/en unknown
- 1981-07-03 ES ES503647A patent/ES8205254A1/en not_active Expired
- 1981-07-03 JP JP56103475A patent/JPS5744668A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2022606A (en) * | 1934-06-08 | 1935-11-26 | Du Pont | Brown disazo dyes |
| FR1355911A (en) * | 1962-03-29 | 1964-03-20 | Basf Ag | Highly concentrated solutions of basic dyes with good stability |
| EP0036553A1 (en) * | 1980-03-22 | 1981-09-30 | BASF Aktiengesellschaft | Method of preparing liquid compositions of basic azo dyestuffs |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0115818A2 (en) * | 1983-02-03 | 1984-08-15 | Bayer Ag | Cationic polyazo-dyestuffs, their stabilized solutions, their preparation and use |
| EP0115818A3 (en) * | 1983-02-03 | 1984-09-12 | Bayer Ag | Cationic polyazo-dyestuffs, their stabilized solutions, their preparation and use |
| EP0341325A1 (en) * | 1988-05-07 | 1989-11-15 | BASF Aktiengesellschaft | Process for the manufacture of liquid preparations of basic azodyes |
| US7488810B2 (en) | 2002-11-28 | 2009-02-10 | Basf Aktiengesellschaft | Method for producing a liquid formulation of salts of sulfoacidic azo dyes |
| WO2005113681A1 (en) * | 2004-05-19 | 2005-12-01 | Basf Aktiengesellschaft | Method for producing a liquid formulation of salts of sulphonic-acid azo dyes |
| WO2005113682A1 (en) * | 2004-05-19 | 2005-12-01 | Basf Aktiengesellschaft | Method for producing liquid adjustments of basic azo dyes |
| US7847073B2 (en) | 2004-05-19 | 2010-12-07 | Basf Aktiengesellschaft | Method for producing a liquid formulation of salts of sulphonic-acid azo dyes |
| CN1957043B (en) * | 2004-05-19 | 2011-03-02 | 巴斯福股份公司 | Method for producing a liquid formulation of salts of sulphonic-acid azo dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3160953D1 (en) | 1983-10-27 |
| ES503647A0 (en) | 1982-06-01 |
| ES8205254A1 (en) | 1982-06-01 |
| DE3025557A1 (en) | 1982-02-04 |
| US4400321A (en) | 1983-08-23 |
| JPS5744668A (en) | 1982-03-13 |
| BR8104262A (en) | 1982-03-23 |
| EP0045840B1 (en) | 1983-09-21 |
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